Electrocatalytic reduction of CO2 at a chemically modified electrode

O’Toole, Terrence R.; Margerum, Lawrence D.; Westmoreland, T. David; Vining, William J.; Murray, Royce W.; Meyer, Thomas J.

doi:10.1039/c39850001416

Cited by 129 publications

(59 citation statements)

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“…27 This behavior is also distinct from that displayed by vinyl substituted Re-bipyridine complexes that can be electrodeposited on electrode surfaces. 45,46 The rapid deposition of Re(BB2)(CO)3Cl onto the working electrode may be due to formation of π−π interactions between the large, planar BODIPY units of the BB2 ligand the glassy carbon surface.…”

Section: Resultsmentioning

confidence: 99%

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

et al. 2014

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The reduction of carbon dioxide to chemical fuels such as carbon monoxide is an important challenge in the field of renewable energy conversion. Given the thermodynamic stability of carbon dioxide, it is difficult to efficiently activate this substrate in a selective fashion and the development of new electrocatalysts for CO2 reduction is of prime importance. To this end, we have prepared and studied a new fac-ReI(CO)3 complex supported by a bipyridine ligand containing ancillary BODIPY moieties ([Re(BB2)(CO)3Cl]). Voltammetry experiments revealed that this system displays a rich redox chemistry under N2, as [Re(BB2)(CO)3Cl] can be reduced by up to four electrons at modest potentials. These redox events have been characterized as the ReI/0 couple, and three ligand based reductions – two of which are localized on the BODIPY units. The ability of the BB2 ligand to serve as a non-innocent redox reservoir is manifest in an enhanced electrocatalysis with CO2 as compared to an unsubstituted Re-bipyridine complex lacking BODIPY units ([Re(bpy)(CO)3Cl]). The second order rate constant for reduction of CO2 by [Re(BB2)(CO)3Cl] was measured to be k = 3400 M−1s−1 at an applied potential of −2.0 V versus SCE, which is roughly three times greater than the corresponding unsubstituted Re-bipyridine homologue. Photophysical and photochemical studies were also carried out to determine if [Re(BB2)(CO)3Cl] was a competent platform for CO2 reduction using visible light. These experiments showed that this complex supports unusual excited state dynamics that precludes efficient CO2 reduction and are distinct from those that are typically observed for fac-ReI(CO)3 complexes.

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Section: Resultsmentioning

confidence: 99%

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

et al. 2014

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“…In the past, the most frequently reported ways to immobilize Re catalysts onto solid electrodes were either the insertion of the molecule into a polymer matrix15–17 or the chemical modification of the ligand with a functional group that allowed polymerization to form a redox polymer 18–20…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Reduction of Carbon Dioxide to Carbon Monoxide by a Polymerized Film of an Alkynyl‐Substituted Rhenium(I) Complex

et al. 2013

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The alkynyl-substituted ReI complex [Re(5,5′-bisphenylethynyl-2,2′-bipyridyl)(CO)3Cl] was immobilized by electropolymerization onto a Pt-plate electrode. The polymerized film exhibited electrocatalytic activity for the reduction of CO2 to CO. Cyclic voltammetry studies and bulk controlled-potential electrolysis experiments were performed by using a CO2-saturated acetonitrile solution. The CO2 reduction, determined by cyclic voltammetry, occurs at approximately −1150 mV versus the normal hydrogen electrode (NHE). Quantitative analysis by GC and IR spectroscopy was used to determine a Faradaic efficiency of approximately 33 % for the formation of CO. Both values of the modified electrode were compared to the performance of the homogenous monomer [Re(5,5′-bisphenylethynyl-2,2′-bipyridyl)(CO)3Cl] in acetonitrile. The polymer formation and its properties were studied by using SEM, AFM, and attenuated total reflectance (ATR) FTIR and UV/Vis spectroscopy.

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“…The products were typically CO under anhydrous conditions or a mixture of CO and formate with added water. A 4-Me-4 0 -vinylbpy derivative of Re(bpy)(CO) 3 Cl [28,29], was incorporated on the surfaces of electrodes by co-electropolymerization with the vinylderivatized complex, [Ru(vbpy) 3 ] 2? (vbpy is 4-vinyl-2,2 0 -bipyridine) where it was shown to be active toward CO 2 reduction to give CO as the dominant product.…”

Section: Co 2 Reduction By Ru Polypyridyl Complexesmentioning

confidence: 99%

Electrocatalytic Reduction of Carbon Dioxide: Let the Molecules Do the Work

et al. 2014

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This review summarizes the development of electrochemical CO 2 reduction catalysts in the UNC Energy Frontier Research Center for Solar Fuels. Two strategies for converting CO 2 to CO or formate have been explored. In one, polypyridyl complexes of Ru(II) have been used to reduce CO 2 to CO in acetonitrile and in acetonitrile/water mixtures. In the absence of CO 2 water is reduced to H 2 by these complexes. With added weak acids in acetonitrile with added water and CO 2 , reduction to syngas mixtures of CO and H 2 is observed. A single polypyridyl complex of Ru(II) has been shown to be both a catalyst for water oxidation and CO 2 reduction in an electrochemical cell for CO 2 splitting into CO and O 2 . In parallel, Ir pincer catalysts have been shown to act as selective electrocatalysts for reducing CO 2 to formate in acetonitrile with added water and in pure water without competition from electrocatalytic H 2 production. Details of the catalytic mechanisms of each have also been investigated.The world's energy future is being driven by increased demand which is currently met by increasing use of fossil fuels with their associated environmental impact through the greenhouse gas effect [1]. With technologies that evolve to become cost effective, renewable energy is the appealing energy source of the future with the sun the ultimate energy source. However, large-scale use of solar energy requires large land areas and a vast energy storage capability for nighttime and on-demand utilization. Natural photosynthesis is appealing with energy conversion through stored biomass but, with typical solar efficiencies of B1 %, is impractical as a source for the high energy densities required to power urban centers and industrial complexes. A long-term solution is potentially available based on ''artificial photosynthesis'' with solar fuels the product, water splitting into H 2 and O 2 or reduction of CO 2 to a carbon fuel or carbon fuel precursor [2]. Solar-driven reduction of CO 2 by water occurs in green plants and photosynthetic bacteria and is an inspiration for the development of an artificial photosynthesis-based equivalent. Given the impressive efficiencies reached with current semiconductor technology for photovotaic devices, far higher efficiencies should be reachable in artificial photosynthesis compared to natural photosynthesis with a target of [10 % being a reasonable goal. The products of artificial photosynthesis are so-called solar fuels, highenergy density molecules with solar energy stored in chemical bonds. As noted above, target reactions are water splitting into hydrogen and oxygen, and reduction of CO 2 to CO, formic acid, methanol or other reduced forms of carbon, with hydrocarbons especially attractive because

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Electrocatalytic reduction of CO2 at a chemically modified electrode

Cited by 129 publications

References 0 publications

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Electrocatalytic Reduction of Carbon Dioxide to Carbon Monoxide by a Polymerized Film of an Alkynyl‐Substituted Rhenium(I) Complex

Electrocatalytic Reduction of Carbon Dioxide: Let the Molecules Do the Work

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